EP0301487B1 - Procédé de protection de matériaux pierreux, marbre, briques et béton contre la dégradation par des agents atmosphériques et polluants ou par des inscriptions murales avec des peintures, encres, etc - Google Patents

Procédé de protection de matériaux pierreux, marbre, briques et béton contre la dégradation par des agents atmosphériques et polluants ou par des inscriptions murales avec des peintures, encres, etc Download PDF

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Publication number
EP0301487B1
EP0301487B1 EP19880112061 EP88112061A EP0301487B1 EP 0301487 B1 EP0301487 B1 EP 0301487B1 EP 19880112061 EP19880112061 EP 19880112061 EP 88112061 A EP88112061 A EP 88112061A EP 0301487 B1 EP0301487 B1 EP 0301487B1
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EP
European Patent Office
Prior art keywords
cf2o
comprised
range
chain
perfluoropolyether
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EP19880112061
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German (de)
English (en)
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EP0301487A3 (en
EP0301487A2 (fr
Inventor
Franco Piacenti
Carlo Manganelli Del Fa'
Giovanni Moggi
Adolfo Pasetti
Andrea Scala
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Solvay Specialty Polymers Italy SpA
Consiglio Nazionale delle Richerche CNR
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Consiglio Nazionale delle Richerche CNR
Ausimont SpA
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Priority claimed from IT21468/87A external-priority patent/IT1223291B/it
Priority claimed from IT8722950A external-priority patent/IT1233420B/it
Application filed by Consiglio Nazionale delle Richerche CNR, Ausimont SpA filed Critical Consiglio Nazionale delle Richerche CNR
Priority to AT88112061T priority Critical patent/ATE80372T1/de
Publication of EP0301487A2 publication Critical patent/EP0301487A2/fr
Publication of EP0301487A3 publication Critical patent/EP0301487A3/en
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Publication of EP0301487B1 publication Critical patent/EP0301487B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4838—Halogenated polymers
    • C04B41/4842—Fluorine-containing polymers
    • C04B41/4846—Perfluoro-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00439—Physico-chemical properties of the materials not provided for elsewhere in C04B2111/00
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/25—Graffiti resistance; Graffiti removing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544—Addition polymer is perhalogenated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]

Definitions

  • the present invention is concerned with a process for the protection of stone materials, marble, bricks and concrete, and of structures made from such materials, from decay caused by atmospheric agents and pollutants or by mural writings with paints, inks and the like.
  • a physical phenomenon which acts on all building materials is that due to the succession of frost and thaw, which causes water absorbed inside the pores of the same material to freeze and the corresponding ice to melt, with changes in specific volume, and stresses which cause fractures, or separation of individual particles which constitute the material.
  • Another chemical-physical phenomenon is the process of dissolution in water of limestone which is present in marble as an essential component, and in stone as a binder, consequently having no cohesion between the granules.
  • US-A-4499146 discloses the use for such a purpose of neutral perfluoropolyethers, i.e. perfluoropolyethers not provided with functional groups.
  • EP-A-192493 and 215492 disclose the use of perfluoropolyethers wherein either one chain end, or both chain ends, are constituted by functional groups, such as amide groups or ester groups.
  • the same European patent applications also disclose the use of functionalized perfluoropolyethers in mixture with neutral perfluoropolyethers.
  • An object of the present invention is to provide a process which supplies an excellent protection both to low- or medium-porosity materials, and to high-porosity materials.
  • Another object is to provide a process which provides a better protection, the amount of protecting agents relative to both functionalized and non-functionalized perfluoropolyethers, being the same.
  • tetrafluoroethylene copolymers suitable for use in the present invention for example, those may be cited, which contain up to 10 mol % of hexafluoropropene and up to 5 mol % of perfluoroalkyl-perfluorovinyl-ethers, in particular perfluoropropyl-perfluorovinyl-ether, used up to an amount of 3 mol %.
  • the average molecular weight of tetrafluoroethylene homopolymers or copolymers is generally within the range of from 100 000 to 2 000 000.
  • the average size of the primary homopolymer or copolymer particles is generally comprised within the range of from 0.05 to 0.5 ⁇ m.
  • the average molecular weight of the perfluoropolyether not containing functional groups is commonly comprised within the range of from 3 000 to 16 000 whereas that of the functionalized perfluoropolyethers or fluoropolyethers is commonly comprised within the range of from 500 to 20 000.
  • Neutral perfluoropolyethers i.e. perfluoropolyethers not bearing functional groups
  • functionalized perfluoropolyethers and fluoropolyethers suitable to be used in the mixture of protective agents of the present invention are e.g. disclosed in above-cited US-A-4499146, and EP-A-192493 and 215492.
  • neutral perfluoropolyethers and functionalized perfluoropolyethers and fluoropolyethers and of their manufacturing process, reference is also made to US patents Nos.
  • Neutral perfluoropolyethers of the following classes may for example be used:
  • bi-functionalized (per)fluoropolyethers belonging to (F), (H), (J) and (K) classes can also be used, as explained in EP-A-215492 in the form of their products of polycondensation with other polycondensible monomers, i.e., e.g., as polyurethanes polyureas, polyesters, polyamides, polyethers, polyimides and polyamic acids.
  • the monofunctional or bifunctional (per)fluoropolyethers belonging to (G), (H), (J) and (K) classes, containing Z3 end groups, i.e., those containing a polymerizable unsaturation of ethylenic type, can be also used in the form of their polymerization products, as disclosed in EP-A-215492.
  • the polytetrafluoroethylene, or its copolymer to be used in the present invention can be obtained by means of known methods. It can be directly synthetized with the desired molecular weight, as described, e.g., by Mc Cane in "Encyclopaedia of Polymer Science and Technology", vol. 13, page 623, Interscience, New York, 1970.
  • the amount of polytetrafluoroethylene or of its copolymer in the mixture of protective agents according to the present invention is comprised within the range of from 2 to 30% by weight relative to the mixture, the mixture preferably containing from 10 to 20% thereof.
  • a neutral perfluoropolyether or a functionalized perfluoropolyether or fluoropolyether is used.
  • both said polyether types are present; in said three-component mixtures, the weight ratio of the functionalized perfluoropolyether or fluoropolyether to the neutral perfluoropolyether is equal to, or higher than, 0.01; said ratio is preferably comprised within the range of from 0.1 to 0.6.
  • neutral or functionalized polyether, or their mixture can be used as such, or dissolved in a chlorofluorocarbon or in a fluorocarbon.
  • Particularly suitable is 1,1,2-trichloro-1,2,2-trifluoro-ethane.
  • the solution usually contains from 30 to 90% by weight of polyether.
  • polytetrafluoroethylene or its copolymer are neither soluble in either functionalized or non-functionalized perfluoropolyethers or fluoropolyethers, nor in said solvents, they are introduced into the mixture in the solid state. More precisely, by suitably stirring, a suspension is prepared of the polymer or copolymer in the liquid phase constituted by the polyether(s) and the possible solvent, and the suspension is applied to the materials or structures to be protected.
  • the application of the suspension of protective agents on the materials or structures is carried out by suitable means: for example, it can be carried out by spraying an atomized - with or without compressed air - liquid stream, or by spreading by brush.
  • the amount of protective mixture to be applied to the surfaces to be protected may vary within wide limits, as a function of the nature of the material to be treated, in particular, of its porosity. Obviously, for porous materials, larger amounts are used. Usually, amounts comprised within the range of from 10 g to 500 g/m2 of surface to be treated are used.
  • the protective composition can be removed from the materials and structures to which it has been applied, by treating such materials and structures first with 1,1,2-trichloro-1,2,2-trifluoroethane in order to remove most of the composition, and then with compressed air, in order to remove the residues of polytetrafluoroethylene or of its copolymer.
  • the present invention also relates to a process for preventing or eliminating the effects of decay caused on materials for the building industry and for linings, by the use of inks, spray paints or brush paints, coloured chalks, posted-up placards and the like.
  • the Applicant has found that by using either a perfluoropolyether, or a fluoropolyether having at least one end group consisting of a functional group capable of forming a chemical and/or physical bond with the material to be protected, in mixture with:
  • tetrafluoroethylene copolymers suitable for use there can be used, e.g. those indicated above.
  • the average molecular weight of the homopolymer or copolymer of tetrafluoroethylene, the average size of the primary particles of homopolymer or copolymer, the average molecular weight of the perfluoropolyether not bearing functional groups, and the average molecular weight of the functionalized perfluoropolyether or fluoropolyether are as indicated above.
  • the perfluoropolyethers not bearing functional groups and the functionalzed perfluoropolyethers may contain oxaperfluoroalkylene units belonging to types (I) to (IX) as described above.
  • the functionalized fluoropolyethers may contain the units (X) and (XI) as described above.
  • polytetrafluoroethylene, or the tetrafluoroethylene copolymer to be used in the present invention can be obtained by the methods indicated above.
  • the amount of polytetrafluoroethylene, or of tetrafluoroethylene copolymers in mixture with protecting agents according to the present invention is comprised within the range of from 2 to 30% by weight relative to the total mixture.
  • the mixture comprises from 10 to 20% thereof.
  • the functionalized polyether either alone, or optionally in admixture with polyethers bearing functional groups, can be used as such, or it can be dissolved in a chlorofluorocarbon or fluorocarbon as indicated above.
  • the weight ratio of the functionalized perfluoropolyether or functionalized fluoropolyethers to neutral perfluoropolyethers is equal to or larger than 0.01; such a ratio is preferably comprised within the range of from 0.1 to 0.6.
  • polytetrafluoroethylene and tetrafluoroethylene copolymers are neither soluble in perfluoropolyethers or fluoropolyethers whether functionalized or not, nor in the above said solvents, they are incorporated into the mixture in the solid state as indicated above.
  • the amount of protecting agent to be applied to the surfaces to be protected is as indicated above.
  • the protecting composition can be removed from the materials and buildings to which it was applied as indicated above.
  • test pieces having a porosity of 1.7% are used.
  • the test pieces have a size of 50 x 50 x 20 mm.
  • Test piece 1 is not treated. Different protective compositions are applied by means of a brush to the other test pieces.
  • variable amounts of neutral perfluoropolyether Fomblin® YR and of polytetrafluoroethylene are applied. (To test piece 5 no polytetrafluoroethylene is applied).
  • the neutral perfluoropolyether Fomblin®YR manufactured by Montefluos S.p.A. has the formula: wherein: R f is CF3 and R′ f is CF3.
  • Its average molecular weight is of approximately 6 500.
  • variable amounts of a mixture of a neutral perfluoropolyether Fomblin® YR and of an amide functionalized perfluoropolyether are applied together with variable amounts of polytetrafluoroethylene (to test piece 9, no polytetrafluoroethylene is applied).
  • the ratio by weight of neutral perfluoropolyether to the amidic perfluoropolyether is of 60:40.
  • amidic perfluoropolyether has the formula: wherein: R f is CF3. Its average molecular weight is of approximately 5,000.
  • Polytetrafluoroethylene is Algoflon® L206 , manufactured by Montefluos S.p.A..
  • the size of the primary particles of polytetrafluoroethylene is comprised within the range of from 0.15 to 0.25 ⁇ m.
  • the amount of protective composition applied by brush-spreading to test pieces 2-9 is expressed as grams per square metre of surface area, and is reported in Table 1A.
  • the efficacy of the treatment is evaluated on the basis of the amount of water absorbed by the various test pieces within 60 minutes and is expressed by the percent ratio:
  • the test is carried out by applying to a face of the test pieces a device constituted by a glass cylinder filled with water, and connected with a graduated micropipette, which allows the amount of water absorbed by the surface of contact with the sample to be measured.
  • a device constituted by a glass cylinder filled with water, and connected with a graduated micropipette, which allows the amount of water absorbed by the surface of contact with the sample to be measured.
  • a device constituted by a glass cylinder filled with water, and connected with a graduated micropipette, which allows the amount of water absorbed by the surface of contact with the sample to be measured.
  • Such equipment is described in the document published by Unesco-Rilem PEM Group with No. 78,182.
  • the reading of the absorbed water is carried out at prefixed time intervals, and the quantity read is expressed as g/cm2 of surface area.
  • compositions according to the present invention yields better results, than the use of either the neutral or functionalized perfluoropolyether alone, although a smaller amount of protective agents is used.
  • the permeability of the protective coatings to water vapour is a necessary feature, in that it enables any water which may be present under the coating to evaporate.
  • test piece is fastened, by means of a sealing agent, to a plexiglas vessel, according to the arrangement as disclosed in EP-A-192493.
  • the assembly constituted by the test piece and the vessel is weighed.
  • the tests are run at the controlled constant temperature of 20°C.
  • the test is discontinued after 144 hours, and the end weight losses are compared to those of the untreated sample, to which a permeability of 100% is attributed.
  • the protective compositions according to the present invention supply a permeability to water vapour slightly lower than that obtained with perfluoropolyether alone.
  • a permeability remains very good, in that the permeability values are regarded as good from 50% up.
  • TABLE 1B Test No. Treated Material Protective Agents (% by weight) Amount of Applied Protective Agents g/m2 Permeability to water 1 Marble None - 100% 5* Marble Fomblin® YR 100% 81 85% 2 " Fomblin® YR 95% + PTFE 5% 45 80% 3 " Fomblin® YR 90% + PTFE 10% 56 80% 4 " Fomblin® YR 85% + PTFE 15% 55 70% * comparative
  • the tests are carried out on a sandstone having a porosity of 8.5%.
  • the modalities are the same as of Example 1, except for the fact that the test of water absorption is carried out in 30 minutes, and the permeability to water vapour is not determined.
  • Example 2 The tests of Example 2 are carried out on a Vicenza stone having a porosity of 30%.
  • mixtures of protective agents according to the present invention give a high treatment efficacy also in case of very porous materials.
  • Example 2 The tests of Example 2 are repeated on a Lecce stone having a porosity of 42%.
  • the tests were carried out on a concrete having 18% of porosity.
  • the material was prepared by starting from: Portland 425 cement, using a water/cement ratio of 0.425 and a cement/inerts (sand and gravel) ratio of 0.3.
  • the protective agent is constituted by a mixture of a neutral perfluoropolyether, a carboxy-functionalized perfluoropolyether and polytetrafluoroethylene.
  • the neutral pefluoropolyether is the same Fomblin® YR as of Example 1.
  • the functionalized perfluoropolyether has the formula: wherein R f is -CF3, and has an average molecular weight of approximately 2 000.
  • the ratio of the functionalized perfluoropolyether relatively to the neutral perfluoropolyether is of 20:80 parts by weight.
  • Mixtures are used, which contain various amounts of Algoflon L206 polytetrafluoroethylene.
  • a slab of Carrara marble was used, whose surface had a porosity of 0.3%.
  • Such a slab had a thickness of 4 cm, with sides of 120x180 cm, and was subdivided into two portions with the same surface area; to one of said portions, an amount of FOMBLIN® Y MET (a perfluoropolyether with perfluoroalkyl end groups by Montefluos S.p.A.) of 80 g/m2 was applied.
  • the application was carried out by means of a brush, after a cleaning of the surface, in order to remove any dust or foreign substances, by means of two successive operations, spaced out by approximately 70 hours.
  • the slab surface treated with the protecting agent was slightly darker and more glossy than the original surface was before the treatment.
  • the test is carried out in the same way as disclosed in Example 1, but the cleaning step (the (b) step) is carried out 90 days later.
  • the cleaning of the parts treated with the protective agent does not yield satisfactory results, due to the persistence of colour areas.
  • a set of plates of Carrara marble with porosity of 1.5% were used, with each one of them being subdivided into two portions of equal surface area; to each of said portions, variable amounts of perfluoroalkyl-terminated perfluoropolyethers of Fomblin® Y type, of perfluoropolyethers with isobutyl ester (IBE) end groups, and of perfluoropolyethers with isobutyl-amide end groups (IBA) were applied.
  • the cleaning tests were carried out 72 hours after the writing test.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Paints Or Removers (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubricants (AREA)

Claims (16)

  1. Un procédé de protection de matériaux pierreux, de marbre, de briques et de béton, ainsi que d'ouvrages obtenus à partir de ces matériaux, contre une dégradation provoquée par les agents atmosphériques et les polluants, par application d'un agent protecteur sur la surface desdits matériaux et ouvrages, caractérisé en ce que l'agent protecteur comprend un mélange:
    (1) de polytétrafluoréthylène, ou d'un copolymère de tétrafluoréthylène contenant jusqu'à 12% en moles d'autres monomères perfluorés, ledit homopolymère ou copolymère étant utilisé sous forme d'une poudre fine et en une quantité de 2 à 30% en poids par rapport au mélange total;
    (2) d'un perfluoropolyéther ne portant pas de groupes fonctionnels, ledit perfluoropolyéther contenant des motifs répétitifs choisis parmi:
    (I) (CF₂-CF₂O) et (CF₂O), ces motifs étant répartis statistiquement sur la chaîne perfluoropolyéther;
    (II)
    Figure imgb0073
     et (CFXO), où X est F ou CF₃,
    lesdits motifs étant répartis statistiquement sur la chaîne;
    (III) (CF₂-CF₂),
    Figure imgb0074
     et (CFXO), où X est F ou CF₃,
    ces motifs étant répartis statistiquement sur la chaîne; ou
    (IV)
    Figure imgb0075
    (V) (CF₂-CF₂-CF₂O);
    (VI)
    Figure imgb0076
     où R"f est un groupe fluoralkylène; n' vaut 0 ou 1;
    a' et b' sont des entiers, et la somme (a'+b') est supérieure ou égale à 2;
    (VII) (CF₂-CF₂O);
    (VIII)
    Figure imgb0077
     où les groupes R"'f, qui sont identiques ou différents, représentent chacun un fluor ou un groupe perfluoralkyle;
    (IX) (CF₂O-CF₂-CF₂O);
    (3) d'un perfluoropolyéther ou un fluoropolyéther, dont l'une des extrémités de chaîne, ou les deux extrémités de chaîne, sont constituées d'un groupe fonctionnel à même de former une liaison chimique et/ou physique avec le matériau à protéger, ou encore d'un produit de polycondensation ou de polymérisation éthylénique du perfluoropolyéther ou du fluoropolyéther fonctionnalisés ci-dessus, ledit fluoropolyéther comportant des motifs choisis parmi:
    (X) (CF₂-CF₂-CF₂O); et
    (XI) (CF₂-CF₂-CH₂O)p'-Riv f-O-(CH₂-CF₂-CF₂O)q'
    où Riv f est un groupe fluoralkylène, et p' et q' valent chacun zéro ou sont des entiers, la somme (p'+q') étant supérieure ou égale à 2.
    et ledit perfluoropolyéther ayant des motifs répétitifs (I) à (IX) tels que définis ci-dessus.
  2. Le procédé selon la revendication 1, caractérisé en ce que la granulométrie moyenne des particules primaires de l'homopolymère ou du copolymère de tétrafluoréthylène est comprise entre 0,05 et 0,5 µm.
  3. Le procédé selon la revendication 1 ou 2, caractérisé en ce que la masse moléculaire moyenne de l'homopolymère ou du copolymère de tétrafluoréthylène est comprise entre 100 000 et 2 000 000.
  4. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la masse moléculaire moyenne du perfluoropolyéther ne portant pas de groupes fonctionnels est comprise entre 3000 et 16 000.
  5. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le perfluoropolyéther ou le fluoropolyéther dont une extrémité de chaîne ou les deux extrémités de la chaîne sont constituées d'un groupe fonctionnel, a une masse moléculaire moyenne comprise entre 500 et 20 000.
  6. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le perfluoropolyéther ne portant pas de groupes fonctionnels est choisi dans l'une des classes suivantes:
    A)
    Figure imgb0078
     où:
    Rf et R'f, qui sont identiques ou différents, sont choisis parmi CF₃, C₂F₅ et C₃F₇; les motifs C₃F₆O (oxytrifluorométhyltrifluoréthylène),
    Figure imgb0079
     et CF₂O étant répartis statistiquement sur la chaîne;
    a est un entier;
    b et c sont des entiers ou valent chacun zéro;
    quand la somme (b+c) est différente de zéro, le rapport a/(b+c) est compris entre 5 et 40;
    la masse moléculaire est comprise entre 4000 et 10 000;
    B) CF₃O-(C₂F₄O)d(CF₂O)e-CF₃
    où les motifs C₂F₄O et CF₂O sont répartis statistiquement sur la chaîne;
    d et e sont des entiers;
    le rapport d/e est compris entre 0,3 et 5;
    la masse moléculaire moyenne est comprise entre 3000 et 16 000;
    C) CF₃O-(C₃F₆O)f(C₂F₄O)g-(CFXO)h-CF₃
    où les motifs C₃F₆O, C₂F₄O et CFXO sont répartis statistiquement sur la chaîne;
    f, g et h sont des entiers;
    le rapport f/(g+h) est compris entre 1 et 50;
    le rapport g/h est compris entre 1 et 10;
    X est F ou CF₃;
    la masse moléculaire moyenne est comprise entre 4000 et 12 000;
    D) R³fO-(CF₂CF₂CF₂O)jR⁴f
    où R³f et R⁴f, identiques ou différents, représentent, chacun, -CF₃ ou C₂F₅, et
    j est un entier ayant une valeur telle que la masse moléculaire moyenne soit comprise entre 4000 et 16 000.
  7. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le perfluoropolyéther ou le fluoropolyéther ayant une extrémité de chaîne ou les deux extrémités de la chaîne constituées d'un groupe fonctionnel à même de former une liaison chimique et/ou physique avec le matériau à protéger est choisi dans l'une des classes suivantes:
    E)
    Figure imgb0080
     où:
    Rf est un groupe perfluoroalkyle ayant 1 à 3 atomes de carbone; les motifs C₃F₆O,
    Figure imgb0081
     et CF₂O étant répartis statistiquement sur la chaîne;
    a est un entier;
    b et c sont des entiers ou valent chacun zéro;
    quand la somme (b+c) est différente de zéro, le rapport a/(b+c) est compris entre 5 et 10;
    D est un groupe -CFX-COZ', où X est F ou CF₃ et Z' est OH, OR⁵ ou NR⁶R⁷, R⁵ étant un groupe alkyle ayant 1 à 8 atomes de carbone, un groupe aromatique, ou un groupe alkylaromatique, le groupe aromatique pouvant être substitué par des groupes alkyles ou des groupes polyéthoxy; R⁶ et R⁷, identiques ou différents, peuvent être chacun un groupe alkyle ayant 1 à 8 atomes de carbone ou un groupe phényle substitué par des groupes alkyles ou des groupes polyéthoxy; la masse moléculaire moyenne est comprise entre 500 et 10 000;
    F) D'-(C₂F₄O)d(CF₂O)e-D'
    où les motifs C₂F₄O et CF₂O sont répartis statistiquement sur la chaîne;
    d et e sont des entiers; le rapport d/e est compris entre 0,3 et 5;
    D' = CF₂-COZ', où Z' a la signification donnée ci-dessus;
    la masse moléculaire moyenne est comprise entre 1000 et 20 000;
    G)
    Figure imgb0082
     où:
    Rf est un groupe perfluoralkyle ayant 1 à 3 atomes de carbone; les motifs C₃F₆O,
    Figure imgb0083
     et CF₂O étant répartis statistiquement sur la chaîne;
    a est un entiers;
    b et c sont des entiers ou valent chacun zéro;
    quand la somme (b+c) est différente de zéro, le rapport a/(b+c) est compris entre 5 et 40;
    p peut valoir 1 ou 2;
    Y est un radical organique pontant bivalent ou trivalent;
    la masse moléculaire moyenne est comprise entre 500 et 10 000;
    Z est un groupe fonctionnel à même de former une liaison chimique et/ou physique avec le matériau à protéger, et est choisi dans le groupe consistant en Z1, Z2, Z3 et Z4, où:
    Z1   est un radical organique non aromatique, non fluoré, ne contenant pas d'atomes d'hydrogène actif, contenant deux hétéroatomes ou plus, identiques ou différents et choisis parmi O, M, S, Se et P, qui sont des donneurs de doublets électroniques et sont situés sur les positions 1-3, 1-4 ou 1-5 les uns par rapport aux autres, ou un radical aromatique contenant éventuellement des hétéroatomes choisis parmi ceux indiqués ci-dessus, à même de former des liaisons de coordination ou datives;
    Z2   est un radical -CONR⁹R¹⁰ ou COOR¹¹, où R¹¹ est un groupe alkyle ayant 1 à 8 atomes de carbone, un groupe aromatique ou un groupe alkylaromatique, le groupe aromatique peut être substitué par des groupes alkyles ou par des groupes polyéthoxy;
    R⁹ et R¹⁰, qui sont identiques ou différents, ont les mêmes significations que R¹¹;
    ou représente un radical
    Figure imgb0084
     où Ar est un groupe aromatique ayant de préférence 6 ou 10 atomes de carbone;
    ou un radical -OH; -NCO;
    Figure imgb0085
     -NHR¹¹; -COR¹¹; -SiR¹²t(OR¹³)3-t
    où R¹² et R¹³, qui sont identiques ou différents, ont les mêmes significations que R¹¹, t valant 0, 1 ou 2;
    Z3   est un radical contenant une insaturation polymérisable du type éthylénique;
    Z4   est un radical appartenant à la classe Z1, contenant un ou plusieurs substituants R¹¹, R¹¹ ayant les significations données ci-dessus.
    H) AO-(C₂F₄O)k(CF₂O)₁-A'
    où les motifs C₂F₄O et CF₂O sont répartis statistiquement sur la chaîne;
    k et l sont des entiers; le rapport k/l est compris entre 0,3 et 5;
    A' = CFX-YZp
    A est A' ou un radical perfluoralkyle ayant 1 à 3 atomes de carbone; p, X, Y et Z ont les mêmes significations que celles indiquées ci-dessus;
    la masse moléculaire est comprise entre 1000 et 20 000;
    J) AO-(C₃F₆O)f(C₂F₄O)g(CFXO)h-A'
    où les motifs C₃F₆O, C₂F₄O et CFXO sont répartis statistiquement sur la chaîne;
    f, g et h sont des entiers; le rapport f/(g+h) est compris entre 1 et 50;
    le rapport g/h est compris entre 1 et 10;
    A, A' et X ont les mêmes significations que celles indiquées ci-dessus;
    la masse moléculaire est comprise entre 500 et 20 000;
    K)
    Figure imgb0086
     où R¹⁴ et R¹⁵, qui sont identiques ou différents, sont chacun choisis parmi H, Cl et F; un atome de fluor dans les fragments -CF₂- pouvant être substitué par H, Cl, un groupe perfluoralcoxy ou un groupe perfluoralkyle;
    quand le composé contient des motifs
    Figure imgb0087
     qui sont différents les uns des autres, ces motifs sont répartis statistiquement sur la chaîne; m est un entier choisi de façon que la masse moléculaire moyenne soit comprise entre 1500 et 8000.
  8. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le radical 23 est choisi parmi les radicaux méthacryle, acryle, cinnamique, vinyle, allyle, vinyléther et allyléther.
  9. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le radical pontant organique Y est choisi parmi:
    -CH₂O-, -CH₂-O-CH₂-, -CH₂(OCH₂CH₂)n- (où n est un entier compris entre 1 et 3), -CF₂-, -CF₂O-, -CH₂-, -CONR¹¹-, -COO-, -COS-, -CO-, -CH₂NR¹¹-, -CH₂S-, où R¹¹ est un groupe alkyle ayant 1 à 8 atomes de carbone, un groupe aromatique ou un groupe alkylaromatique, le groupe aromatique pouvant être substitué par des groupes alkyles ou des groupes polyéthoxy.
  10. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le mélange d'agents protecteurs contient de 10 à 20% en poids de l'homopolymère ou du copolymère de tétrafluoréthylène.
  11. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que le perfluoropolyéther ne portant pas de groupes fonctionnels et/ou le perfluoropolyéther ou le fluoropolyéther dont une extrémité de chaîne ou les deux extrémités de la chaîne sont constituées d'un groupe fonctionnel, sont utilisés sous forme de leur solution dans un chlorofluorocarbone ou dans un fluorocarbone.
  12. Le procédé selon la revendication 11, caractérisé en ce que le chlorofluorocarbone est le 1,1,2-trichloro-1,2,2-trifluoroéthane.
  13. Le procédé selon l'une ou plusieurs des revendications précédentes, caractérisé en ce que la quantité d'agents protecteurs appliqués sur les matériaux ou ouvrages à protéger est comprise entre 10 et 500 g/m² d'aire à traiter.
  14. Un procédé de protection de matériaux pour l'industrie du bâtiment et les parements, contre les peintures, encres et analogues, qui consiste à appliquer sur la surface de ces matériaux, ayant une porosité non supérieure à 40%, un revêtement comprenant un perfluoropolyéther ou un fluoropolyéther dont une extrémité de chaîne ou les deux extrémités de chaîne sont constituées d'un groupe fonctionnel à même de former une liaison chimique et/ou physique avec le matériau à protéger, où ledit perfluoropolyéther contient des motifs oxaperfluoralkylène choisis parmi les classes suivantes:
    (I) (CF₂-CF₂O) et (CF₂O), ces motifs étant répartis statistiquement sur la chaîne perfluoropolyéther;
    (II)
    Figure imgb0088
     et (CFXO), où X est F ou CF₃, lesdits motifs étant répartis statistiquement sur la chaîne;
    (III) (CF₂-CF₂),
    Figure imgb0089
     et (CFXO), où X est F ou CF₃,
    ces motifs étant répartis statistiquement sur la chaîne; ou
    (IV)
    Figure imgb0090
    (V) (CF₂-CF₂-CF₂O);
    (VI)
    Figure imgb0091
     où R"f est un groupe fluoralkylène; n' vaut 0 ou 1;
    a' et b' sont des entiers, et la somme (a'+b') est supérieure ou égale à 2;
    (VII) (CF₂-CF₂O);
    (VIII)
    Figure imgb0092
     où les groupes R"'f, qui sont identiques ou différents, représentent chacun un fluor ou un groupe perfluoralkyle;
    (IX) (CF₂O-CF₂-CF₂O);
    et/où le perfluoropolyéther contient les motifs suivants:
    (X) (CF₂-CF₂-CF₂O); ou
    (XI) (CF₂-CF₂-CH₂O)p'-Riv f-O-(CH₂-CF₂-CF₂O)q'
    où:
    Riv f est un groupe fluoralkylène, et
    p' et q' valent chacun zéro ou sont de entiers, et la somme (p'+q') est supérieure ou égale à 2;
    ledit perfluoropolyéther ou fluoropolyéther étant utilisé en mélange avec:
    (1) 2 à 30% en poids, par rapport au total des composants du revêtement, d'un polytétrafluoréthylène ou d'un copolymère de tétrafluoréthylène contenant jusqu'à 12% en mole d'autres monomères perfluorés, ledit homopolymère ou copolymère étant utilisé sous forme d'une poudre fine; et éventuellement
    (2) un perfluoropolyéther comportant des groupes terminaux perfluoralkyles.
  15. Le procédé selon la revendication 14, dans lequel le polytétrafluoréthylène ou un copolymère de tétrafluoréthylène est présent en une quantité de 10 à 20% en poids.
  16. Le procédé selon la revendication 14 ou 15, dans lequel le copolymère de tétrafluoréthylène contient jusqu'à 10% en moles d'hexafluoropropène et jusqu'à 5% en moles de perfluoroalkyleperfluorovinyléther.
EP19880112061 1987-07-27 1988-07-26 Procédé de protection de matériaux pierreux, marbre, briques et béton contre la dégradation par des agents atmosphériques et polluants ou par des inscriptions murales avec des peintures, encres, etc Expired - Lifetime EP0301487B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88112061T ATE80372T1 (de) 1987-07-27 1988-07-26 Verfahren zum schuetzen von steinmaterialien, marcor, ziegel und beton gegen verfall durch atmosphaerische und verunreinigende agenzien oder durch graffiti und dergleichen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IT21468/87A IT1223291B (it) 1987-07-27 1987-07-27 Procedimento per la protezione di materiali lapidei, marmo, laterizi e cemento dagli agenti e dagli inquinanti atmosferici
IT2146887 1987-07-27
IT8722950A IT1233420B (it) 1987-12-11 1987-12-11 Procedimento per la protezione delle superfici lapidee, contro il degrado causato dalle scritture murali effettuate con vernici, inchiostri e simili
IT2295087 1987-12-11

Publications (3)

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EP0301487A2 EP0301487A2 (fr) 1989-02-01
EP0301487A3 EP0301487A3 (en) 1989-07-26
EP0301487B1 true EP0301487B1 (fr) 1992-09-09

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US (1) US4902538A (fr)
EP (1) EP0301487B1 (fr)
JP (1) JPH01111785A (fr)
DE (1) DE3874454T2 (fr)
ES (1) ES2034057T3 (fr)
GR (1) GR3006396T3 (fr)

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IT1227692B (it) * 1988-12-19 1991-04-23 Ausimont Srl Procedimento per la protezione di materiali lapidei, marmo, laterizi e cemento dagli agenti e dagli inquinanti atmosferici
US6127000A (en) * 1997-10-10 2000-10-03 North Carolina State University Method and compositions for protecting civil infrastructure
WO2001062687A1 (fr) 2000-02-22 2001-08-30 E.I. Dupont De Nemours And Company Procede de protection de pierre a l'aide d'urethanne fluore
WO2001087801A2 (fr) * 2000-05-15 2001-11-22 E.I. Dupont De Nemours And Company Procede de protection de la pierre avec des fluoropolymeres essentiellement amorphes
WO2002004383A1 (fr) 2000-07-07 2002-01-17 E.I. Dupont De Nemours And Company Procede pour la protection de roches via des fluoropolymeres sensiblement amorphes
ES2306654T3 (es) * 2000-10-27 2008-11-16 THE PROCTER & GAMBLE COMPANY Composiciones y metodos para tratar superficies.
US6790924B2 (en) * 2001-02-22 2004-09-14 E. I. Du Pont De Nemours And Company Method for protection of stone with fluorinated urethane
EP1262464B1 (fr) 2001-05-29 2004-09-29 3M Innovative Properties Company Poudre de mortier qui a été melangée avec de composés de fluor
US20030176524A1 (en) * 2002-01-23 2003-09-18 Swingle Robert S. Coating having graffiti resistance
US20060047032A1 (en) * 2004-09-01 2006-03-02 Miller Chandra T Anionic/cationic masonry sealing systems
DE112005003849B4 (de) * 2004-09-14 2013-06-20 NOK Klüber Co., Ltd. Verwendung einer perfluorpolyether-ölzusammensetzung als schmiermittelzusammensetzung
CA2593694A1 (fr) * 2004-12-30 2006-07-13 3M Innovative Properties Company Articles comprenant une couche superficielle a base de composes fluores et procedes correspondants
US20070044685A1 (en) * 2005-09-01 2007-03-01 Harvinder Khanna Mosaic marble flooring and driveway system
JP4793443B2 (ja) * 2006-04-20 2011-10-12 Ｎｏｋクリューバー株式会社 含油軸受用潤滑剤組成物
ES2322740B1 (es) 2007-05-10 2010-04-06 Asociacion Española De Fabricantes De Ladrillos Y Tejas De Arcilla Cocida, Hispalyt Lamina flexible de ladrillos para la construccion de elementos arquitectonicos, y procedimiento de fabricacion de dicha lamina.
CN110903056B (zh) * 2018-09-18 2022-04-01 武汉源锦商品混凝土有限公司 一种高强度自密实清水混凝土及其制备方法

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GB1087283A (en) * 1965-03-18 1967-10-18 Du Pont Lubricant grease
US4094911A (en) 1969-03-10 1978-06-13 Minnesota Mining And Manufacturing Company Poly(perfluoroalkylene oxide) derivatives
IT1135597B (it) * 1981-02-24 1986-08-27 Montedison Spa Impiego di perfluoropolieteri per la protezione di materiali da inquinamento
IT1207492B (it) 1985-02-22 1989-05-25 Montefluos Spa Impiego di derivati dei perfluoropo lieteri per la protezione dei materiali lapidei dagli agenti atmosferici
IT1201470B (it) * 1985-09-24 1989-02-02 Montefluos Spa Impiego di derivati dei perfluoropolieteri per la protezione dei materiali lapidei dagli agenti atmosferici

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US4902538A (en) 1990-02-20
DE3874454D1 (de) 1992-10-15
GR3006396T3 (fr) 1993-06-21
EP0301487A3 (en) 1989-07-26
DE3874454T2 (de) 1993-04-08
EP0301487A2 (fr) 1989-02-01
ES2034057T3 (es) 1993-04-01
JPH01111785A (ja) 1989-04-28

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